WO2024143315A1 - 吸水性樹脂組成物及び止水材並びにケーブル - Google Patents

吸水性樹脂組成物及び止水材並びにケーブル Download PDF

Info

Publication number
WO2024143315A1
WO2024143315A1 PCT/JP2023/046537 JP2023046537W WO2024143315A1 WO 2024143315 A1 WO2024143315 A1 WO 2024143315A1 JP 2023046537 W JP2023046537 W JP 2023046537W WO 2024143315 A1 WO2024143315 A1 WO 2024143315A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
absorbent resin
resin composition
mass
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2023/046537
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
和 ▲高▼橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Seika Chemicals Co Ltd
Original Assignee
Sumitomo Seika Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Seika Chemicals Co Ltd filed Critical Sumitomo Seika Chemicals Co Ltd
Priority to KR1020257021446A priority Critical patent/KR20250130304A/ko
Priority to JP2024567833A priority patent/JPWO2024143315A1/ja
Priority to CN202380087318.5A priority patent/CN120380092A/zh
Publication of WO2024143315A1 publication Critical patent/WO2024143315A1/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
    • H01B7/285—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable by completely or partially filling interstices in the cable
    • H01B7/288—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable by completely or partially filling interstices in the cable using hygroscopic material or material swelling in the presence of liquid

Definitions

  • the present invention relates to a water-absorbent resin composition, a water-stopping material, and a cable.
  • Water-absorbent resins have excellent water absorption capabilities and can exert a water-stopping effect, so they are known to be applicable to various applications where water-stopping is required.
  • water-absorbent resins are used as water-stopping materials for communication cables such as optical cables and power cables.
  • Patent Document 1 discloses a technology in which a water-stopping material made by sealing a water-absorbent sheet containing a water-absorbent resin in an exterior material makes it difficult for the gel of the water-absorbent resin that swells after absorbing water to leak out.
  • the present invention has been made in consideration of the above, and aims to provide a water-absorbing resin composition with excellent heat resistance, and a water-stopping material and cable that contain the water-absorbing resin composition.
  • a water-absorbent resin composition comprising a benzimidazole compound represented by the formula: Item 2 Item 2.
  • Item 3 The water-absorbent resin composition according to item 1 or 2, wherein the content of the benzimidazole compound is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the water-absorbent resin particles.
  • the water-absorbent resin composition according to item 2 wherein the content of the metal chelating agent is 0.001 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the water-absorbent resin particles.
  • Item 5 Item 5.
  • Item 6 Item 6.
  • a water-stopping material comprising the water-absorbent resin composition according to any one of items 1 to 5.
  • Item 7 Item 7.
  • a cable comprising the waterproof material according to item 6.
  • the water-absorbent resin composition of the present invention has excellent heat resistance.
  • FIG. 2 is a schematic diagram of a measuring device used for measuring the swelling height of a water-absorbing resin composition.
  • Water-absorbent resin composition contains water-absorbent resin particles and a benzimidazole compound represented by the following general formula (1).
  • R 1 represents a methyl group or a hydrogen atom
  • R 2 represents a methyl group, an amino group, a methylthio group, a phenyl group or a hydrogen atom.
  • the water-absorbent resin composition of the present invention contains water-absorbent resin particles and a benzimidazole compound represented by the formula (1), and therefore has excellent heat resistance. Specifically, the water-absorbent resin composition of the present invention is unlikely to cause a decrease in gel viscosity even when placed in a high-temperature environment in a swollen gel state, that is, the gel is unlikely to deteriorate even in a high-temperature environment. Therefore, the water-absorbent resin composition of the present invention can be suitably used for various water-stopping materials, and is particularly suitable as a water-stopping material for cables.
  • whether or not the composition has excellent heat resistance can be judged from the values of gel viscosity A and gel viscosity retention rate S after 4 days in an environment of 90 ⁇ 2°C, as described below.
  • the water-absorbing resin composition of the present invention contains the benzimidazole compound represented by the general formula (1), which allows the water-absorbing resin composition of the present invention to have excellent heat resistance.
  • Examples of the benzimidazole compound represented by formula (1) include benzimidazole, 2-aminobenzimidazole, 1-methylbenzimidazole, 2-methylbenzimidazole, 2-amino-1-methylbenzimidazole, 2-phenylbenzimidazole, and 2-(methylthio)benzimidazole.
  • the benzimidazole compound represented by formula (1) can be obtained by a known manufacturing method, or can be obtained from a commercial product, etc.
  • the type of water-absorbent resin particles can be, for example, a wide variety of known water-absorbent resin particles.
  • the water-absorbent resin particles preferably have a structure in which a polymer of a water-soluble ethylenically unsaturated monomer is crosslinked.
  • the water-absorbent resin composition can have excellent heat resistance.
  • the polymer of a water-soluble ethylenically unsaturated monomer may have a structure crosslinked by an internal crosslinking agent described below, or may have a structure crosslinked by a post-crosslinking agent described below instead of or in addition to the internal crosslinking agent.
  • the degree of neutralization of the water-soluble ethylenically unsaturated monomer by the alkaline neutralizing agent in order to increase the osmotic pressure of the resulting water-absorbent resin and thereby improve the water-absorbing performance, it is generally preferable that the degree of neutralization of all acid groups possessed by the water-soluble ethylenically unsaturated monomer is 10 to 100 mol%, and more preferably 30 to 80 mol%.
  • the water-absorbent resin particles can be produced, for example, by a production method including a step of carrying out a polymerization reaction using a raw material containing the water-soluble ethylenically unsaturated monomer (hereinafter, the "polymerization step").
  • Polymerization reactions carried out in the polymerization step include, for example, reversed-phase suspension polymerization, aqueous solution polymerization, and emulsion polymerization. It is preferable to use reversed-phase suspension polymerization in the polymerization step because it is easy to adjust the 30-second swelling height to a specified range.
  • Reverse-phase suspension polymerization is, for example, a method in which a poorly soluble monomer is suspended in a dispersion medium in the presence of a dispersion stabilizer and polymerized.
  • the reversed-phase suspension polymerization method may be a multi-stage polymerization in which the monomer is polymerized in multiple stages, or may be, for example, a two-stage polymerization. In a multi-stage polymerization, the first polymerization reaction is called the first stage, and the monomers added stepwise after the first stage polymerization are called the second stage, the third stage, and so on.
  • an internal crosslinking agent can be used as necessary. This allows the polymer obtained in the polymerization step to have a structure in which the inside is crosslinked by the internal crosslinking agent. Therefore, when the water-absorbent resin particles have a crosslinked structure inside the polymer, this internal crosslinked structure is formed when the water-soluble ethylenically unsaturated monomer is polymerized.
  • the crosslinking agent used for crosslinking inside the polymer is called an internal crosslinking agent to distinguish it from a post-crosslinking agent.
  • the temperature of the polymerization reaction can be set appropriately depending on the type and amount of radical polymerization initiator used, and can be set, for example, at 20 to 110°C, and preferably at 40 to 90°C.
  • the reaction time can be set, for example, at least 0.1 hours and no more than 4 hours.
  • an aqueous solution containing a water-soluble ethylenically unsaturated monomer, which has been neutralized as necessary, a thickener, a radical polymerization initiator, and an internal crosslinking agent is added to a dispersion medium in which a polymeric dispersion stabilizer is dissolved, and then a surfactant is added to create a suspension state.
  • the water-absorbing resin composition of the present invention may contain a metal chelating agent.
  • the metal chelating agent is preferably one or more selected from the group consisting of phosphonic acid-based metal chelating agents and metal chelating agents having an aminocarboxylic acid moiety.
  • the water absorbent resin composition is more likely to have excellent heat resistance.
  • a particularly preferred metal chelating agent having an aminocarboxylic acid moiety is ethylenediamine-N,N'-disuccinic acid trisodium salt, and particularly preferred phosphonic acid-based metal chelating agents are ethylenediaminetetramethylenephosphonic acid pentasodium salt and diethylenetriaminepentamethylenephosphonic acid heptasodium salt.
  • the metal chelating agent can be obtained by known manufacturing methods, or it can be obtained from commercial products, etc.
  • the content ratio of the water absorbent resin particles and the benzimidazole compound (compound represented by formula (1)) can be 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the water absorbent resin particles from the viewpoint of easily improving heat resistance.
  • the content of the metal chelating agent with respect to 100 parts by mass of the water absorbent resin particles is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, and particularly preferably 2 parts by mass or more.
  • the content of the metal chelating agent with respect to 100 parts by mass of the water absorbent resin particles is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • the water absorbent resin composition of the present invention may contain the metal chelating agent in addition to the water absorbent resin particles and the benzimidazole compound. In this case, the heat resistance is further improved.
  • the content of the metal chelating agent can be 0.001 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the water absorbent resin particles.
  • the water-absorbent resin composition of the present invention may consist of only the water-absorbent resin particles, the metal chelating agent, the benzimidazole compound, and silica, or may consist of only the water-absorbent resin particles, the metal chelating agent, and the benzimidazole compound.
  • the median particle size of the water-absorbent resin composition of the present invention is, for example, 10 to 500 ⁇ m, preferably 30 to 300 ⁇ m, more preferably 50 to 250 ⁇ m, and even more preferably 100 to 200 ⁇ m.
  • the shape of the water-absorbent resin of the present invention may be various shapes, such as, for example, spherical, pulverized, granular, elliptical, scaly, rod-like, or lump-like.
  • the method of applying or impregnating the water-absorbent resin composition to the substrate can be, for example, by applying or impregnating the substrate with a dispersion in which the water-absorbent resin composition is dispersed in an organic solvent.
  • an adhesive can be used in combination to increase the adhesion.
  • aqueous liquid was added to a separable flask and stirred for 10 minutes, and then a surfactant solution prepared by heating and dissolving 0.782 g of sucrose stearate with HLB3 (Ryoto Sugar Ester S-370, Mitsubishi Chemical Foods Corporation) in 7.04 g of n-heptane in a 20 mL vial was further added, and the inside of the system was thoroughly replaced with nitrogen while stirring at a stirrer speed of 450 rpm, after which the flask was immersed in a 70° C. water bath to raise the temperature, and polymerization was carried out for 60 minutes to obtain a first-stage polymerization slurry liquid.
  • HLB3 Hydrophilic acid
  • the swelling height of the water-absorbent resin composition was measured by a swelling height measuring device X shown in FIG. 1.
  • the swelling height measuring device X shown in FIG. 1 includes a moving distance measuring device 1, a concave circular cup 2 (height 45 mm, outer diameter 90 mm. Depth of the recess 40 mm, inner diameter of the recess 80 mm), a plastic convex circular cylinder 3 (outer diameter 79 mm, 60 through holes 7 with a diameter of 2 mm evenly arranged on the contact surface with the water-absorbent resin composition), and a nonwoven fabric 4 (liquid-permeable nonwoven fabric with a basis weight of 11 g/m 2 ).
  • the displacement of the distance moved by the convex circular cylinder 3 can be measured in units of 0.01 mm by a laser beam 6.
  • the concave circular cup 2 can uniformly spray a predetermined amount of the water-absorbent resin composition.
  • the convex circular cylinder 3 can uniformly apply a load of 90 g to the sample water-absorbent resin composition 5.
  • the water level of the ion-exchanged water was checked every 3 seconds from the start of the introduction of the ion-exchanged water, and the ion-exchanged water was intermittently poured in so as to maintain the water level near the height of the flat surface of the flat part of the convex circular cylinder 3.
  • the gel viscosity of the water absorbent resin composition was measured by adjusting the temperature of the swollen gel to 25 ⁇ 0.5° C. and using Vismetron (Shibaura Systems VDH2 type, rotor No. 5, rotation speed 10 rpm). The gel viscosity measurement was performed in a state where the gel was placed in a 200 mL glass beaker with an inner diameter of 64 mm ⁇ to a height of 65 mm.
  • Gel viscosity retention rate S (B / A) x 100 (I)
  • the gel viscosity retention rate S was calculated by the following formula (I): A represents the gel viscosity (mPa ⁇ s) after 4 days in an environment at 90 ⁇ 2°C, and B represents the gel viscosity (mPa ⁇ s) after 9 days in an environment at 90 ⁇ 2°C.
  • the gel viscosity A and gel viscosity retention rate S after 4 days in an environment of 90 ⁇ 2° C. were used as indicators of heat resistance.
  • Table 1 shows the evaluation results of the water-absorbent resin compositions obtained in each Example and Comparative Example. It was confirmed that the water-absorbent resin compositions obtained in each Example had high gel viscosity after 4 days under heating conditions of 90°C, and had high gel viscosity retention. This result shows that the water-absorbent resin compositions obtained in each Example have excellent heat resistance in a swollen state, and supports the idea that the gel state can be maintained for a long period of time even in the environment in which power cables are used or in a similar environment.
  • the water-absorbent resin composition obtained in the examples has excellent heat resistance in a swollen state and can be suitably used as a water-stopping material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)
PCT/JP2023/046537 2022-12-26 2023-12-26 吸水性樹脂組成物及び止水材並びにケーブル Pending WO2024143315A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020257021446A KR20250130304A (ko) 2022-12-26 2023-12-26 흡수성 수지 조성물 및 지수재 및 케이블
JP2024567833A JPWO2024143315A1 (cs) 2022-12-26 2023-12-26
CN202380087318.5A CN120380092A (zh) 2022-12-26 2023-12-26 吸水性树脂组合物和止水材料以及电缆

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022208814 2022-12-26
JP2022-208814 2022-12-26

Publications (1)

Publication Number Publication Date
WO2024143315A1 true WO2024143315A1 (ja) 2024-07-04

Family

ID=91718066

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/046537 Pending WO2024143315A1 (ja) 2022-12-26 2023-12-26 吸水性樹脂組成物及び止水材並びにケーブル

Country Status (4)

Country Link
JP (1) JPWO2024143315A1 (cs)
KR (1) KR20250130304A (cs)
CN (1) CN120380092A (cs)
WO (1) WO2024143315A1 (cs)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6148610U (cs) * 1984-09-01 1986-04-01
JP2004210924A (ja) * 2002-12-27 2004-07-29 Sumitomo Seika Chem Co Ltd 吸水性樹脂組成物
WO2020203722A1 (ja) * 2019-03-29 2020-10-08 住友精化株式会社 吸水性樹脂及び止水材
WO2021075459A1 (ja) * 2019-10-18 2021-04-22 住友精化株式会社 防臭剤組成物、吸収体及び吸収性物品

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6354062B2 (ja) 2013-01-07 2018-07-11 株式会社アイ・イー・ジェー 保護管付地下埋設ケーブル用止水材および止水方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6148610U (cs) * 1984-09-01 1986-04-01
JP2004210924A (ja) * 2002-12-27 2004-07-29 Sumitomo Seika Chem Co Ltd 吸水性樹脂組成物
WO2020203722A1 (ja) * 2019-03-29 2020-10-08 住友精化株式会社 吸水性樹脂及び止水材
WO2021075459A1 (ja) * 2019-10-18 2021-04-22 住友精化株式会社 防臭剤組成物、吸収体及び吸収性物品

Also Published As

Publication number Publication date
JPWO2024143315A1 (cs) 2024-07-04
KR20250130304A (ko) 2025-09-01
CN120380092A (zh) 2025-07-25

Similar Documents

Publication Publication Date Title
JP6126655B2 (ja) 吸水性樹脂粒子の製造方法
TWI485163B (zh) Production method of water-absorbent resin particles and water-absorbent resin particles
JP5099899B2 (ja) 吸水性樹脂の製造方法
JP5383048B2 (ja) 加水分解安定性の後架橋された超吸収体
US8940845B2 (en) Method for producing water-absorbing resin
WO2016148153A1 (ja) 吸水性樹脂および吸水剤
WO2024063154A1 (ja) 吸水性樹脂組成物、止水材及びケーブル
JP7633929B2 (ja) 吸水性樹脂及び止水材
JPH04120176A (ja) 吸水剤及びその製造方法
WO2024143315A1 (ja) 吸水性樹脂組成物及び止水材並びにケーブル
WO2019074099A1 (ja) 吸水性樹脂及び吸収性物品
JP7625513B2 (ja) 吸水性樹脂及び止水材
WO2024063155A1 (ja) 吸水性樹脂組成物、止水材及びケーブル
WO2025205166A1 (ja) 吸水性樹脂粒子、止水材およびケーブル
TWI736927B (zh) 吸水性樹脂組成物、吸水性樹脂與其製作方法
CN110358117B (zh) 吸水性树脂组成物、吸水性树脂与其制作方法
KR102873778B1 (ko) 흡수성 수지 및 지수재
JP2009154155A (ja) 吸水剤の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23912094

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024567833

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: CN2023800873185

Country of ref document: CN

Ref document number: 202380087318.5

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 202517064626

Country of ref document: IN

WWP Wipo information: published in national office

Ref document number: 202517064626

Country of ref document: IN

Ref document number: 202380087318.5

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2023912094

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE